US4557946A - Moisture impermeability or organosilicone films - Google Patents
Moisture impermeability or organosilicone films Download PDFInfo
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- US4557946A US4557946A US06/500,810 US50081083A US4557946A US 4557946 A US4557946 A US 4557946A US 50081083 A US50081083 A US 50081083A US 4557946 A US4557946 A US 4557946A
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- organosilicone
- permeation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/62—Plasma-deposition of organic layers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Definitions
- the invention relates to a method of controlling the water permeability of a coating, and more particularly it relates to a method of controlling the water permeability of an organosilicone coating applied to a substrate.
- moisture-permeation barriers are well known in the art, and indeed such barriers are in every day use. Typically, they are employed for corrosion protection, passivation of electronic circuits, etc. Thus, for instance, in dielectrics utilized in hostile environmental applications, the electrical conductivity of such dielectrics is substantially affected by the presence of humidity through its mobilization of otherwise immobile ions and it is often desirable and/or necessary to provide a barrier which will reduce moisture permeation, enhancing the performance and the lifetime of the device.
- water-permeation barriers such as polymers, and they have received extensive use. However, they do also suffer from some inadequacies, such as poor adhesion, shrinkage, water sensitivity, and too high water permeation for certain uses.
- organosilicone polymers when applied under certain process parameters in the form of thin plasma polymerized coatings, can be controlled to provide a certain physical structure which can substantially decrease water permeation into the plasma polymer/substrate composite, while at the same time adhering well to the substrate.
- These coatings are relatively inexpensive to apply in a controlled, reproducible manner and can be applied to industrial processes, thereby overcoming many of the disadvantages previously associated with moisture barriers.
- substrate denotes any suitable solid, polymeric or non-polymeric, natural or synthetic , into which it is desired to reduce moisture permeation.
- types of substrates may vary very widely and in the following description, reference is made to one type of substrate as being only illustrative of the type of substrates that may be used, and as only being illustrative of the type of problems which can be alleviated by the present invention.
- any suitable organosilicone monomer having a sufficiently high vapour pressure may be employed in the process.
- Suitable monomers are basically those which have a vapour pressure in excess of 0.01 of a Torr.
- the organosilicone coating applied on the substrate is plasma polymerized hexamethyldisiloxane.
- the polymers are deposited using a plasma generator.
- plasma generators are well known in the art, and reference may be made to the literature for this purpose.
- a low pressure plasma or "glow discharge" is preferred.
- RF or microwave frequencies is preferred in the present process; in principle, frequencies ranging from 0-100 GHz can be used.
- the composition of the film between its "organic” and “inorganic” components can be varied to give desired permeation properties.
- An example is seen in FIG. 1.
- power levels between 0.01 watts/cu. cm 3 . to about 10 watts/cu. cm 3 . can be utilized, while a true substrate temperature of between 25° C. and 1000° C. may be employed.
- a true substrate temperature of between 25° C. and 1000° C.
- FIG. 1 is a graph showing the overall composition of plasma polymerized organosilicone films, prepared from hexamethyldisilazane, as a function of substrate temperature during deposition, T s .
- FIG. 2 is a graph showing the rise in effective T s corresponding to the microwave power applied
- FIG. 3 is a graph showing the effect of increased power density on the moisture permeation rate
- FIG. 4 is a graph showing the moisture permeation rate corresponding to T s and P;
- FIG. 5 is a graph showing the permeation coefficient vs. P and T s ;
- FIG. 6 shows a test carried out for measuring the moisture permeation rate
- FIG. 7 is a comparative graph showing performance of other plasma polymers as moisture barriers.
- FIG. 1 shows the effect of substrate temperature T s , on the composition of plasma polymerized organosilicone films, made from hexamethyldisilazane in this instance.
- the "organic” (carbon) content is seen to decrease systematically with increasing T s , the silicon content is seen to rise.
- T s substrate temperature
- the "true" T s under this condition is 480° C.; the effectiveness of increased power density, therefore, is only partially related to an increase in T s .
- Table 1 hereunder, compares permeation data for various polymers.
- the table shows permeation coefficients ( ⁇ ), diffusion coefficients (D, in cm 2 /sec.), solubility coefficients (S in std cm 3 /cm 3 . cm Hg), and water vapor concentrations in the sample (C, in g H 2 O/g polymer) for the materials indicated.
- Moisture permeation rates were additionally measured using ASTM E 96-53T, "Water Vapor Transmission of Materials in Sheet Form" in the following manner.
- a "Kapton" film (either bare, or plasma-coated on one side) was placed over a small glass dish as shown in the drawings.
- Straightforward additivity relationships well known in the field of permeation, were used to separate the ⁇ contribution of the plasma polymer layer, which was found to vary from 2.3 ⁇ 10 -10 at 500 ⁇ to 3.1 ⁇ 10 -10 at 5000 ⁇ .
- FIG. 7 shows water permeation rates attained with other plasma polymers, and as will be noted, the results are clearly not up to the standards attained with plasma polymerized organosilicone coatings according to the present invention.
- the adhesion of the coatings to the substrates is also of particular interest.
- the adhesion of the coatings was tested by the simple "Scotch tape” peel test. Thus, a small piece of "Scotch” brand adhesive tape was pressed to the surface, then peeled off. If the polymer film did not lift off the substrate, the adhesion was deemed satisfactory.
- This peel test was carried out in connection with various substrates, including "Kapton H". It was found that films deposited at T s ⁇ 25° C. usually adhere rather poorly, but that beyond a certain elevated T s value, adhesion is excellent. Table 2 below shows the substrate temperatures for 5000 ⁇ thick films. It is to be noted that all films adhere well to "Kapton" for T s ⁇ 180° C.
Abstract
Description
TABLE 1 ______________________________________ Typical Permeation Parameters for Water Near Room Temperature Material Type π D S C ______________________________________ Epoxy ˜10.sup.-7 ˜10.sup.-7 ˜1 ˜0.01 Polyimide ˜10.sup.-8 ˜10.sup.-9 ˜10 ˜0.02 Fluorocarbon ˜10.sup.-9 ˜10.sup.-8 ˜0.1 ˜0.0001 Polyimide/plasma- ˜10.sup.-9 ˜10.sup.-9 ˜1 ˜0.001 polymerized hexamethyl- disiloxane ______________________________________
TABLE 2 ______________________________________ T.sub.s values for Adhesion of 5000 Å Plasma-polymer films on various substrate materials Monomer Substrate T.sub.s (°C.) ______________________________________ Hexamethyl- Glass 170-200 disiloxaneStainless Steel 200 Kapton 150 Hexamethyl- Glass 170-200 disalazaneStainless Steel 200 Kapton 150 Silane Glass 180-200 Kapton 180Ethylene Glass 200 Kapton 150-170 Styrene Glass 170-200 Kapton 170 Tetrafluoro- Glass 150ethylene Kapton 25 Hexafluoro- Glass 150 butene-2Kapton 25 ______________________________________
Claims (7)
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US06/500,810 US4557946A (en) | 1983-06-03 | 1983-06-03 | Moisture impermeability or organosilicone films |
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US06/500,810 US4557946A (en) | 1983-06-03 | 1983-06-03 | Moisture impermeability or organosilicone films |
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Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5224441A (en) * | 1991-09-27 | 1993-07-06 | The Boc Group, Inc. | Apparatus for rapid plasma treatments and method |
US5364666A (en) * | 1993-09-23 | 1994-11-15 | Becton, Dickinson And Company | Process for barrier coating of plastic objects |
US5422185A (en) * | 1992-04-14 | 1995-06-06 | Mitsubishi Petrochemical Co., Ltd. | Olefin resin-based articles having gas barrier properties |
US5560963A (en) * | 1991-10-07 | 1996-10-01 | Ford Motor Company | Low pressure plasma treatment of an article surface |
US5866069A (en) * | 1994-11-03 | 1999-02-02 | Johnson & Johnson Medical Inc. | Liquid repellant silicone-treated gas-permeable material for sterilization |
US5904952A (en) * | 1987-07-15 | 1999-05-18 | The Boc Group, Inc. | Method of plasma enhanced silicon oxide deposition |
US6054379A (en) * | 1998-02-11 | 2000-04-25 | Applied Materials, Inc. | Method of depositing a low k dielectric with organo silane |
US6203898B1 (en) | 1997-08-29 | 2001-03-20 | 3M Innovatave Properties Company | Article comprising a substrate having a silicone coating |
US6287990B1 (en) * | 1998-02-11 | 2001-09-11 | Applied Materials, Inc. | CVD plasma assisted low dielectric constant films |
US6303523B2 (en) * | 1998-02-11 | 2001-10-16 | Applied Materials, Inc. | Plasma processes for depositing low dielectric constant films |
US6399489B1 (en) | 1999-11-01 | 2002-06-04 | Applied Materials, Inc. | Barrier layer deposition using HDP-CVD |
US20030049388A1 (en) * | 2001-09-10 | 2003-03-13 | Seon-Mee Cho | Silicon carbide deposited by high density plasma chemical-vapor deposition with bias |
US6558409B1 (en) * | 2001-09-28 | 2003-05-06 | Tyco Healthcare Group Lp | Plasma treated surgical needles and methods for their manufacture |
US6593247B1 (en) | 1998-02-11 | 2003-07-15 | Applied Materials, Inc. | Method of depositing low k films using an oxidizing plasma |
US6593655B1 (en) | 1998-05-29 | 2003-07-15 | Dow Corning Corporation | Method for producing hydrogenated silicon oxycarbide films having low dielectric constant |
US6660656B2 (en) | 1998-02-11 | 2003-12-09 | Applied Materials Inc. | Plasma processes for depositing low dielectric constant films |
US6667553B2 (en) | 1998-05-29 | 2003-12-23 | Dow Corning Corporation | H:SiOC coated substrates |
US6709721B2 (en) | 2001-03-28 | 2004-03-23 | Applied Materials Inc. | Purge heater design and process development for the improvement of low k film properties |
US20040086725A1 (en) * | 1999-04-07 | 2004-05-06 | Bertrand Jaccoud | Packaging laminate with gas and aroma barrier properties |
US6784119B2 (en) | 1998-02-11 | 2004-08-31 | Applied Materials Inc. | Method of decreasing the K value in SIOC layer deposited by chemical vapor deposition |
US6869666B2 (en) | 2001-05-02 | 2005-03-22 | 3M Innovative Properties Company | Controlled-puncture films |
CN102388160A (en) * | 2009-03-26 | 2012-03-21 | 琳得科株式会社 | Molded body, method for producing same, electronic device member, and electronic device |
US20140065395A1 (en) * | 2007-02-28 | 2014-03-06 | The Boeing Company | Barrier coatings for polymeric substrates |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3518108A (en) * | 1967-06-08 | 1970-06-30 | Bell Telephone Labor Inc | Polymer coating by glow discharge technique and resulting product |
US3822298A (en) * | 1971-11-11 | 1974-07-02 | G Phillipps | Preparation of 3alpha-hydroxy-5alpha-steroids |
JPS538669A (en) * | 1976-07-13 | 1978-01-26 | Kogyo Gijutsuin | Method of prevention of dissolving of additive agents contained in polyvinyl chloride resin |
US4137365A (en) * | 1975-11-21 | 1979-01-30 | Nasa | Oxygen post-treatment of plastic surfaces coated with plasma polymerized silicon-containing monomers |
US4242188A (en) * | 1978-03-23 | 1980-12-30 | Japan Synthetic Rubber Co., Ltd. | Method for controlling plasma chemical reactions |
US4260647A (en) * | 1979-06-13 | 1981-04-07 | Rca Corporation | Method of depositing an abrasive layer |
-
1983
- 1983-06-03 US US06/500,810 patent/US4557946A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3518108A (en) * | 1967-06-08 | 1970-06-30 | Bell Telephone Labor Inc | Polymer coating by glow discharge technique and resulting product |
US3822298A (en) * | 1971-11-11 | 1974-07-02 | G Phillipps | Preparation of 3alpha-hydroxy-5alpha-steroids |
US4137365A (en) * | 1975-11-21 | 1979-01-30 | Nasa | Oxygen post-treatment of plastic surfaces coated with plasma polymerized silicon-containing monomers |
JPS538669A (en) * | 1976-07-13 | 1978-01-26 | Kogyo Gijutsuin | Method of prevention of dissolving of additive agents contained in polyvinyl chloride resin |
US4242188A (en) * | 1978-03-23 | 1980-12-30 | Japan Synthetic Rubber Co., Ltd. | Method for controlling plasma chemical reactions |
US4260647A (en) * | 1979-06-13 | 1981-04-07 | Rca Corporation | Method of depositing an abrasive layer |
Cited By (47)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5904952A (en) * | 1987-07-15 | 1999-05-18 | The Boc Group, Inc. | Method of plasma enhanced silicon oxide deposition |
US5364665A (en) * | 1991-09-27 | 1994-11-15 | The Boc Group, Inc. | Method for rapid plasma treatments |
US5224441A (en) * | 1991-09-27 | 1993-07-06 | The Boc Group, Inc. | Apparatus for rapid plasma treatments and method |
US5560963A (en) * | 1991-10-07 | 1996-10-01 | Ford Motor Company | Low pressure plasma treatment of an article surface |
US5422185A (en) * | 1992-04-14 | 1995-06-06 | Mitsubishi Petrochemical Co., Ltd. | Olefin resin-based articles having gas barrier properties |
US5824198A (en) * | 1993-09-23 | 1998-10-20 | Becton, Dickinson And Company | Process for barrier coating of plastic objects |
US5616369A (en) * | 1993-09-23 | 1997-04-01 | Becton, Dickinson And Company | Process for barrier coating of plastic objects |
US5364666A (en) * | 1993-09-23 | 1994-11-15 | Becton, Dickinson And Company | Process for barrier coating of plastic objects |
US5866069A (en) * | 1994-11-03 | 1999-02-02 | Johnson & Johnson Medical Inc. | Liquid repellant silicone-treated gas-permeable material for sterilization |
US6348237B2 (en) | 1997-08-29 | 2002-02-19 | 3M Innovative Properties Company | Jet plasma process for deposition of coatings |
US7189436B2 (en) | 1997-08-29 | 2007-03-13 | 3M Innovative Properties Company | Flash evaporation-plasma coating deposition method |
US6203898B1 (en) | 1997-08-29 | 2001-03-20 | 3M Innovatave Properties Company | Article comprising a substrate having a silicone coating |
US20050003098A1 (en) * | 1997-08-29 | 2005-01-06 | 3M Innovative Properties Company | Flash evaporation-plasma coating deposition method |
US20020102361A1 (en) * | 1997-08-29 | 2002-08-01 | 3M Innovative Properties Company | Jet plasma process and apparatus for deposition of coatings and the coatings thereof |
US6287990B1 (en) * | 1998-02-11 | 2001-09-11 | Applied Materials, Inc. | CVD plasma assisted low dielectric constant films |
US20080044557A1 (en) * | 1998-02-11 | 2008-02-21 | Wai-Fan Yau | Low dielectric constant film produced from silicon compounds comprising silicon-carbon bond |
US6348725B2 (en) | 1998-02-11 | 2002-02-19 | Applied Materials, Inc. | Plasma processes for depositing low dielectric constant films |
US7651725B2 (en) | 1998-02-11 | 2010-01-26 | Applied Materials, Inc. | Low dielectric constant film produced from silicon compounds comprising silicon-carbon bond |
US6537929B1 (en) | 1998-02-11 | 2003-03-25 | Applied Materials, Inc. | CVD plasma assisted low dielectric constant films |
US6541282B1 (en) | 1998-02-11 | 2003-04-01 | Applied Materials, Inc. | Plasma processes for depositing low dielectric constant films |
US7560377B2 (en) | 1998-02-11 | 2009-07-14 | Applied Materials, Inc. | Plasma processes for depositing low dielectric constant films |
US6562690B1 (en) | 1998-02-11 | 2003-05-13 | Applied Materials, Inc. | Plasma processes for depositing low dielectric constant films |
US6593247B1 (en) | 1998-02-11 | 2003-07-15 | Applied Materials, Inc. | Method of depositing low k films using an oxidizing plasma |
US6784119B2 (en) | 1998-02-11 | 2004-08-31 | Applied Materials Inc. | Method of decreasing the K value in SIOC layer deposited by chemical vapor deposition |
US6596655B1 (en) | 1998-02-11 | 2003-07-22 | Applied Materials Inc. | Plasma processes for depositing low dielectric constant films |
US6660663B1 (en) | 1998-02-11 | 2003-12-09 | Applied Materials Inc. | Computer readable medium for holding a program for performing plasma-assisted CVD of low dielectric constant films formed from organosilane compounds |
US6660656B2 (en) | 1998-02-11 | 2003-12-09 | Applied Materials Inc. | Plasma processes for depositing low dielectric constant films |
US6054379A (en) * | 1998-02-11 | 2000-04-25 | Applied Materials, Inc. | Method of depositing a low k dielectric with organo silane |
US7074708B2 (en) | 1998-02-11 | 2006-07-11 | Applied Materials, Inc. | Method of decreasing the k value in sioc layer deposited by chemical vapor deposition |
US20050156317A1 (en) * | 1998-02-11 | 2005-07-21 | Applied Materials, Inc. | Low dielectric constant film produced from silicon compounds comprising silicon-carbon bonds |
US6730593B2 (en) | 1998-02-11 | 2004-05-04 | Applied Materials Inc. | Method of depositing a low K dielectric with organo silane |
US6303523B2 (en) * | 1998-02-11 | 2001-10-16 | Applied Materials, Inc. | Plasma processes for depositing low dielectric constant films |
US6593655B1 (en) | 1998-05-29 | 2003-07-15 | Dow Corning Corporation | Method for producing hydrogenated silicon oxycarbide films having low dielectric constant |
US6667553B2 (en) | 1998-05-29 | 2003-12-23 | Dow Corning Corporation | H:SiOC coated substrates |
US20040086725A1 (en) * | 1999-04-07 | 2004-05-06 | Bertrand Jaccoud | Packaging laminate with gas and aroma barrier properties |
US7115310B2 (en) * | 1999-04-07 | 2006-10-03 | Tetra Laval Holdings & Finance S.A. | Packaging laminate with gas and aroma barrier properties |
US6399489B1 (en) | 1999-11-01 | 2002-06-04 | Applied Materials, Inc. | Barrier layer deposition using HDP-CVD |
US6713390B2 (en) | 1999-11-01 | 2004-03-30 | Applied Materials Inc. | Barrier layer deposition using HDP-CVD |
US6709721B2 (en) | 2001-03-28 | 2004-03-23 | Applied Materials Inc. | Purge heater design and process development for the improvement of low k film properties |
US6869666B2 (en) | 2001-05-02 | 2005-03-22 | 3M Innovative Properties Company | Controlled-puncture films |
US6926926B2 (en) | 2001-09-10 | 2005-08-09 | Applied Materials, Inc. | Silicon carbide deposited by high density plasma chemical-vapor deposition with bias |
US20030049388A1 (en) * | 2001-09-10 | 2003-03-13 | Seon-Mee Cho | Silicon carbide deposited by high density plasma chemical-vapor deposition with bias |
US6558409B1 (en) * | 2001-09-28 | 2003-05-06 | Tyco Healthcare Group Lp | Plasma treated surgical needles and methods for their manufacture |
US20140065395A1 (en) * | 2007-02-28 | 2014-03-06 | The Boeing Company | Barrier coatings for polymeric substrates |
US9403992B2 (en) * | 2007-02-28 | 2016-08-02 | The Boeing Company | Barrier coatings for polymeric substrates |
CN102388160A (en) * | 2009-03-26 | 2012-03-21 | 琳得科株式会社 | Molded body, method for producing same, electronic device member, and electronic device |
CN102388160B (en) * | 2009-03-26 | 2015-06-10 | 琳得科株式会社 | Molded body, method for producing same, electronic device member, and electronic device |
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